CN101521286B - High discharge capacity lithium battery - Google Patents

High discharge capacity lithium battery Download PDF

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Publication number
CN101521286B
CN101521286B CN2009101331551A CN200910133155A CN101521286B CN 101521286 B CN101521286 B CN 101521286B CN 2009101331551 A CN2009101331551 A CN 2009101331551A CN 200910133155 A CN200910133155 A CN 200910133155A CN 101521286 B CN101521286 B CN 101521286B
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battery
separator
fes
particle size
electrode
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CN101521286A (en
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J·W·马普尔
M·W·温普尔
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Energizer Brands LLC
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Eveready Battery Co Inc
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Abstract

The present invention relates to a high discharge capacity lithium battery, particularly to a lithium/iron disulfide electrochemical battery cell with a high discharge capacity. The cell has a lithiumnegative electrode, an iron disulfide positive electrode and a nonaqueous electrolyte. The iron disulfide of the positive electrode has a controlled average particle size range which allows the elect rochemical cells to exhibit desired properties in both low and high rate applications. In various embodiments, the iron disulfide particles are wet milled, preferably utilizing a media mill or milled utilizing a non-mechanical mill such as a jet mill, which reduces the iron disulfide particles to a desired average particle size range for incorporation into the positive electrode.

Description

High discharge capacity lithium battery
It is that April 1, application number in 2005 are 200580044452.9, denomination of invention is divided an application for what the application of " high discharge capacity lithium battery " was submitted to that the application is based on the applying date.
Technical field
The present invention relates to electrochemical cell, especially have the anodal battery of cathode of lithium and ferrous disulfide.In one embodiment, positive pole comprises the ferrous disulfide particle, and it has specific little average particle size particle size, and this can make electrochemical cell demonstrate underload and high load capacity is used desired performance.Form the ferrous disulfide particle through wet method or dry method, this makes its particle size be reduced to predetermined size range.In a preferred method of the invention, the working medium grinder grinds the cathode slurry that contains the ferrous disulfide particle, and this makes the ferrous disulfide particle be reduced to and is attached to average particle size particle size desired in the positive pole.In a more preferred embodiment, in being attached to positive pole before, use jet grinding to handle the ferrous disulfide particle.
Background of invention
As the used compact power of the electronic device with high power work requirement, lithium battery (the containing metal lithium is as the battery of negative electrode active material) becomes more and more welcome.The lithium battery of general consumption comprises lithium/manganese dioxide (Li/MnO 2) and lithium/iron disulfide (Li/FeS 2) battery, it has the nominal voltage of 3.0 and 1.5 volts per cell respectively.
The battery with bigger discharge capacity is constantly made every effort to design by battery manufacturer.This can be through minimizing by the occupied interior volume of battery of shell (comprise sealing with exhaust), maximizes the obtainable inner volume of active material thus and realize.Yet, always exist physical constraints to maximum internal volume.
Another kind method be in improving battery design and material with the increase discharge capacity.How the best this point that realizes possibly depend on the discharge requirement of battery-powered device at least in part.For having the device that small-power requires, the quantity of active material is very important often, and for the device with high-power requirement, discharging efficiency is often more important.Lithium battery usually is used for high-power device, because they can have fabulous discharging efficiency when high power discharge.
Usually, along with the increase of discharge power, battery discharge efficient descends rapidly.Therefore, for high-power, it is preferential that big discharging efficiency is provided.This usually means that use contains the design of less active material, has therefore sacrificed the capacity of low-power and underload discharge.For example, for good high power discharge efficient, with respect to the volume of electrode, the high interfacial surface area between negative pole (anode) and anodal (negative electrode) is desired.This is usually through using the electrode assemblie that spiral twines to realize, wherein long, thin electrode band is intertwined with the form of coil.Only if electrod composition has high conductivity, otherwise so long thin electrode often need extend many current-collectors along the length and the width of electrode band.The high interfacial surface area of electrode also means the more spacer material of needs so that positive and negative electrode is electrically insulated from each other.Because usually set the largest outer dimension of battery by the size and dimension of battery case in industrial standard or the equipment, increase electrode interface surface area also looks like and refers to reduce the quantity of available active electrode material.
For being high and the battery of low-power purposes design, the input of reduction battery active material is compared for the battery that only designs for higher power applications with the maximization high power performance and is not more expected.For example, 1.5 volts of Li/FeS of AA type 2(FR6 type) be designed to high power applications as photoflash lamp and digital still camera and be used for replacing 1.5 volts of alkaline Zn/MnO of AA type of using always in low-power device more 2Battery.In above-mentioned situation, importantly maximize the input capacity of high power discharge efficient and battery.Though be desirably in any battery maximization electrode input capacity usually, the relative importance that is made in like this in the battery of lower-wattage purposes is bigger.
For maximization active material input in battery and alleviate and increase of the influence of electrode interface surface area to it, expectation be to use spacer material, the latter occupies the least possible inner volume in battery.Do like this and exist physical constraints.Separator must stand battery manufacturing process and not damage; The migration of enough electric insulations and ion between anode and the negative electrode is provided, and does like this and will when battery carries out processing, transportation, storage and the use of normal and expection abnormality, not form the defective that causes internal short-circuit between anode and negative electrode.
The separator performance can be improved to improve intensity and anti-damage property in many aspects.Instance is disclosed in United States Patent (USP) 5,952,120; 6,368,742; In 5,667,911 and 6,602,593.Yet the change of doing for gaining in strength also possibly have adverse effect to the separator performance, part based on as cell chemistry, electrode design and characteristic, battery manufacturing process, expection battery use, expection is stored and factors such as behaviour in service.
For some cell chemistry, the quantity of maximization active material possibly be difficult more in battery.In lithium battery, when the reaction of active cathode material and lithium to produce the product of cumulative volume greater than the reactant volume, the expansion of electrode assemblie has produced additional force in battery.These power possibly cause battery case to expand and produce short circuit through separator.The possible solution of these problems comprises that the material that uses firm (usually thicker) is as the inert component in battery case and the battery; Compare with battery, use the obtainable inner volume of above-mentioned active material in the further limit battery of these active materials with low volumetric reaction product.For Li/FeS 2Battery, another possible solution be at United States Patent (USP) 4,379, and open in 815, it is through making FeS 2Mix to come balance cathode expansion and anode shrink with another active material.Above-mentioned active cathode material comprises CuO, Bi 2O 3, Pb 2Bi 2O 5, P 3O 4, CoS 2With its mixture.Yet, other active material is added to the electricity and the discharge characteristic that possibly influence battery in the cathode mix.
Just constantly manage to improve discharge capacity as battery manufacturers, they are also constantly being worked to improve other battery characteristics, like fail safe and reliability; Make battery more tolerate internal short-circuit have help above both.Can know from above-mentioned discussion and to learn, possibly in the maximization discharge capacity, have the opposite effect for improving the change that the internal short-circuit tolerance made.
Used pyrite or ferrous disulfide (FeS in cathodes for electrochemical cells 2) usually from by pulverizing, heat treatment and dry grinding natural crystal to particle size 20-30 micron (μ m).The reactivity of particle and air and moisture has limited fineness of grind.Along with particle size reduces, its surface area increases and weathering.Weathering is a kind of oxidizing process, and wherein ferrous disulfide and moisture and air reaction form ferric sulfate.Efflorescence causes acid increasing and the electro-chemical activity reduction.Thereby little pyrite particle possibly cause fire at the enough heats of generation between the heat of oxidation in process operation.The used ferrous disulfide particle of prior art possibly have such particle size, it is near about 80 microns final cathode thickness, because the inconsistency of dry grinding process causes.
The dry grinding process of ferrous disulfide is generally undertaken by mining company or agent, has wherein produced lot of materials.The ferrous disulfide of transport point processing and common the storage reach for a long time, and it can be used by battery industry then.Therefore, between the storage life, above-mentioned oxidation and weathering generation and material degradation.In addition, big ferrous disulfide particle size possibly influence like processes such as calenderings, make that base material is out of shape, the bonding fracture of coating-base material, and separator damages the fault that causes.
Summary of the invention
In view of above consideration, the purpose of this invention is to provide a kind of lithium battery with discharge capacity of raising.Another object of the present invention provides the lithium battery of a kind of high-energy-density (the interface discharge capacity is than interface electrode volume).Another object of the present invention provides a kind of Li/FeS with high interface electrode surface area 2Battery, it has the discharge capacity of raising when low power discharge, and does not have to sacrifice the discharging efficiency when high power discharge, preferably, a kind of battery that when high load capacity and underload discharge, has the discharge capacity of raising.Another purpose of the present invention provides Li/FeS 2Battery, it has the cathode interface capacity of increase and has improved energy density and good internal short-circuit tolerance.
Other purpose of the present invention provides a kind of electrochemical cell, and it has and contains less average particle size particle size FeS 2The positive pole of particle.Further purpose provides a kind of electrochemical cell, and it has the underload and the high load capacity properties of product of increase.Another purpose provides a kind of electrochemical cell, and it keeps long high voltage output.Purpose further of the present invention provides the method that produces electrochemical cell (particularly anodal), and, said method comprising the steps of: formation contains FeS for this reason 2The slurries of particle and wetting agent; Use grinder, particularly medium grinder to reduce FeS 2The average particle size particle size of particle and utilize these slurries to form positive pole subsequently.Another object of the present invention provides has anodal electrochemical cell; Said positive pole comprises the ferrous disulfide particle; Utilize like processes such as jet grindings, this particle has been milled to the average particle size particle size of expectation, does not wherein produce heat basically and has obtained narrow particle size distribution.
The present invention has satisfied above-mentioned purpose and has overcome the above-mentioned shortcoming of prior art.
Therefore, of the present inventionly relate in one aspect to a kind of electrochemical cell, it comprises: shell; The negative pole band, it comprises lithium metal; Anodal band, it comprises the active material mixture, and electrolyte, and it comprises at least a salt that places the nonaqueous electrolyte in the shell that is dissolved in; And separator, it places between negative pole and the positive pole; The ratio of the cathode interface capacity of this battery and electrode assemblie interface volume is 710mAh/cm at least 3
Another aspect of the present invention relates to a kind of electrochemical cell, and it comprises: shell; Negative pole, the anodal electrolyte interior with placing shell; And separator, it places between negative pole and the positive pole.Shell comprises cylindrical vessel, and its lid that has integrally closed bottom, initial open top end, the sidewall that between bottom and top, extends and place the top is to seal this battery; The form of negative pole is to have the band on two main relatively surfaces and comprise lithium metal; Anodal form is to have the band on two main relatively surfaces and comprise the active material mixture, and active material comprises the ferrous disulfide greater than 50wt%; Electrolyte comprises that one or more are dissolved in the salt in the non-aqueous organic solvent; Negative pole forms the cylindrical electrode assembly that spiral twines with anodal and separator, and wherein radially-outer surface is arranged to adjoin the inner surface of container side wall; Electrode assemblie has the interface volume; Just having the interface capacity; The ratio of anodal interface capacity and electrode assemblie interface volume is 710mAh/cm at least 3Separator is to have containing of vertical and horizontal of a poly microporous barrier, average thickness less than 22 μ m and in vertical and horizontal tensile stress be at least 1.0kgf/cm.
Another aspect of the present invention relates to a kind of electrochemical cell, and it comprises: shell; Negative pole, the anodal electrolyte interior with placing shell; And separator, it places between negative pole and the positive pole.This battery is cylindrical FR6 type Li/FeS 2Battery, it has the electrode assemblie of the spiral winding that has electrode assemblie interface volume; Battery has the interface capacity of 3500mAh at least; Separator is to contain polyethylene and the average thickness microporous barrier less than 22 μ m; Tensile stress in vertical and horizontal is 2.0kgf/cm at least; Dielectric breakdown voltage is at least 2400 volts, and maximum effective aperture is 0.08 μ m-0.20 μ m, and the BET specific area is 4.0-15m 2/ g.
Another aspect of the present invention relates to a kind of electrochemical cell, and it comprises: shell; Negative pole, the anodal electrolyte interior with placing shell; And separator, it places between negative pole and the positive pole.This battery is cylindrical FR6 type Li/FeS 2Battery, it has the electrode assemblie of the spiral winding that has electrode assemblie interface volume; Separator is to contain polyethylene and the average thickness microporous barrier less than 22 μ m, and the tensile stress in vertical and horizontal is at least 2.0, and dielectric breakdown voltage is at least 2400 volts, and maximum effective aperture is 0.08 μ m-0.20 μ m; Positive pole comprises active material, and it contains the ferrous disulfide of 95wt% at least; With battery can, when when 200mA continuous discharge to 1.0 lies prostrate, the discharge capacity of 2950mAh at least is provided, when when 1000mA continuous discharge to 1.0 lies prostrate, the discharge capacity of 2600mAh at least is provided.
Another aspect of the present invention relates to a kind of electrochemical cell, and it comprises: shell; Negative pole, it comprises lithium; Positive pole, it comprises active material, and said active material comprises the ferrous disulfide greater than 49wt%; The average particle size particle size of said ferrous disulfide is the about 19 μ m of about 1-; Electrolyte mixture, it comprises at least a salt that places the nonaqueous electrolyte in the shell that is dissolved in; And separator, it places between negative pole and the positive pole.
Another aspect of the present invention relates to a kind of electrochemical cell, and it comprises: shell; Negative pole, it comprises lithium; Positive pole, it comprises active material, and said active material comprises the ferrous disulfide greater than 49wt%; Electrolyte mixture, it comprises at least a salt that places the nonaqueous electrolyte in the shell that is dissolved in; And separator, it places between negative pole and the positive pole, and wherein (a) electrolytical conductivity is 1-25 μ m greater than 2.5mS/cm and separator thickness; Or (b) electrolytical conductivity is 1-19 μ m greater than the average particle size particle size of 2.5mS/cm and ferrous disulfide; Or (c) separator thickness is that the average particle size particle size of 1-25 μ m and ferrous disulfide is 1-19 μ m.
Another aspect of the present invention relates to a kind of method for preparing negative electrode; May further comprise the steps: form slurries; These slurries comprise wetting agent and the average particle size particle size ferrous disulfide particle greater than 20 μ m; The medium grinder grinding milk that use contains abrasive media is reduced to the average particle size particle size of 1-19 μ m with the particle size with the ferrous disulfide particle, and the cathode slurry of grinding is applied to cathode substrate forming negative electrode, and dried cathode.
Another aspect of the present invention relates to a kind of electrochemical cell, and it comprises: shell; Negative pole, it comprises lithium; Positive pole, it comprises active material, and said active material comprises the ferrous disulfide greater than 49wt%; Electrolyte mixture, it comprises at least a salt that places the nonaqueous electrolyte in the shell that is dissolved in; And separator, it places between negative pole and the positive pole, and wherein this battery is a FR6 type battery, and at room temperature according to 2/28 second * 10/ hour DSC of 1500/650mW test, it has at least 320 minutes discharge time to 1.05 volts.
Through with reference to following specification, claim and accompanying drawing, those skilled in the art will further understand and understand these and other characteristic of the present invention, advantage and purpose.
Unless otherwise mentioned, as used herein, following term is as giving a definition: active material: one or more compounds, and it is the part of battery discharge reaction and helps discharge capacity of the cell, comprises the impurity and a small amount of other part of existence; The active material mixture: the solid electrode mixtures of material, it does not comprise current-collector and electrode cable, comprises electrode active material; Average particle size particle size: the average diameter of the volume distributed median of composition sample (MV); Can use that to be equipped with model be that the model of 9320 big volume recirculator (LVR) (volume 4L) is measured as the Microtrac Honeywell grain size analysis appearance of X-100.This method of measurement is utilized sonicated to come broken agglomerate and is prevented agglomeration again.Weighing about 2.0 restrains samples and puts into the 50ml beaker.20ml deionized water and 2 surfactants (1%Aerosol OT solution by the 10%Aerosol OT of the 10ml in the 100ml deionized water (can available from Fisher Scientific) preparation, wherein makes solution fully mix); Stir the beaker sample solution, preferably use stirring rod.With deionized water big volume recirculator is filled to certain level, and sample is transferred to from beaker in the recirculator bowl.Use wash bottle that any residual sample particle is flushed in the recirculator bowl.Made sample recirculation one minute, and began then to measure.Be FeS 2Particle is imported following parameter: transparent grain-nothing (absorption); Spherical particle-nothing; Fluid refracting rate-1.33; Experimental period-60 second; Capacity, discharge:, use amp hr (Ah) or milliampere-hour (mAh) expression usually at the actual capacity that interdischarge interval is carried by battery; Capacity; Input: the theoretical capacity of electrode; The weight that equals every kind of active material in the electrode multiply by the theoretical specific capacity of this active material, and wherein the theoretical specific capacity of every kind of active material is confirmed by following computing formula: [(96,487 amperes-second/moles)/(every mole of active material gram number)] * (every mole of active material electron number)/(3600 seconds/hour) * (1000 milliampere-hours/amp hr) (Li=3862.0mAh/g for example; S=1672.0mAh/g, FeS 2=893.6mAh/g, CoS 2-871.3mAh/g, CF x=864.3mAh/g, CuO=673.8mAh/g, C 2F=623.0mAh/g, FeS=609.8mAh/g, CuS=560.7mAh/g, Bi 2O 3=345.1mAh/g, MnO 2=308.3mAh/g, Pb 2Bi 2O 5=293.8mAh/g and FeCuS 2-292.1mAh/g); Capacity, battery interface: less in negative pole and the positive electrode capacity; Capacity; Electrode interface: total contribution of the theoretical discharge capacity of electrode pair battery; Total amount based on active material contained in all batteries exoelectrical reaction mechanism and active material mixture that part of that is adjacent to the active material in the comparative electrode; Suppose all active material complete reactions; Usually represent (only active material that adjoins in the comparative electrode in two of the electrode band main surfaces wherein, only the active material on the electrode side (material on the solid collector plate side or be the half the material of thickness of electrode under the situation that does not have the solid collector plate) is included among the confirming of interface capacity) with Ah or mAh; Electrode assemblie: the combination of negative pole, positive pole and separator and any insulating material that combines with it, external packing, band etc., but get rid of any independent electric lead that invests active material, active material mixture or current-collector; Electrode spacing: in adjacent negative pole and the distance between the positive pole; Electrode load: the active material mixture dry weight of per unit electrode surface areas, usually with every square centimeter of (g/cm of gram 2) expression; The electrode filling rate: the active material dry weight of per unit electrode surface areas is divided by the theoretical active material mixture dry weight of per unit electrode surface areas, and the real density based on the solid material in the mixture is typically expressed as percentage; Folding electrode: be attached to the electrode band in the assembly through folding, wherein the length direction of this band perhaps is parallel to each other or crosses one another; Interfacial level, electrode assemblie: the average height parallel interface surface of electrode in the assembly with longitudinal axis battery; The interface volume, electrode assemblie: the volume in the battery case that is limited area of section and electrode assemblie interfacial level perpendicular to the battery longitudinal axis at container (container) inside surface of side wall place; Nominal: by the value of manufacturer's defined, it has characterized this characteristic or the expectable content of performance; Percentage discharge: the percentage of the rated capacity of taking away from battery at interdischarge interval; Room temperature: about 20 ℃-Yue 25 ℃; The electrode that spiral twines: through being attached to the electrode band in the assembly, for example around mandrel or central core along its length or width winding; And voidage; Electrode assemblie: the amount in the electrode assemblie space of per unit interfacial level; The cumulative volume of the electrode assemblie element through from the volume of electrode assemblie interface, deducting atresia included in the interfacial level and the solid portion of porous electrode component element confirms that (microporosity separator, insulation film, band etc. are assumed that atresia and incompressible; Use the real density of these elements and the volume that total actual volume is confirmed porous electrode), use cm usually 3/ cm representes.
Description of drawings
Through studying detailed description of the invention carefully and combine accompanying drawing, the present invention will be understood preferably and other characteristic and advantage will become cheer and bright, wherein:
Fig. 1 is the embodiment of electrochemical cell of the present invention;
Fig. 2 is such chart, and it has shown the result of conduct in the shock-testing (ImpactTest) of the FR6 battery of the partial discharge of the function of the voidage of the per unit height of interfacial level inner electrode assembly;
Fig. 3 a has set forth and has contained prior art FeS 2The SEM microphoto of the part of the positive pole of particle (amplifying 1000 times);
Fig. 3 b sets forth to contain and utilizes the prepared FeS of medium milling method of the present invention 2The SEM microphoto of the part of the positive pole of particle (amplifying 1000 times);
Fig. 4 has shown the curve chart as the cathode efficiency of using for DSC of the function of separator thickness, it is directed against be some groups constructed have different separator thickness, a FeS 2The FR6 type battery that average particle size particle size and electrolyte are formed;
Fig. 5 is the chart as the anode voltage of the function of depth of discharge percentage, and what it was directed against is to contain prior art FeS 2Electrochemical cell, contain the FeS of medium milling 2The battery of particle and the FeS that contains jet grinding 2The battery of particle and
Fig. 6 is the chart as the cell voltage of the function of the percent of discharge degree of depth, and what it was directed against is to contain prior art FeS 2Electrochemical cell, contain the FeS of medium milling 2The battery of particle and the FeS that contains jet grinding 2The battery of particle.
Embodiment
Battery of the present invention has the anode of containing metal lithium as negative active core-shell material.Anode and negative electrode all are the forms of band, thereby they provide with respect to contain the high interfacial surface area for the volume of the electrode of active material linking together in the electrode assemblie.Interfacial surface area is high more, and current density is low more, and it is just good more to export powerful battery capacity during for discharge.This battery also has the ratios of cathode interface capacity and electrode assemblie interface volume, and it is at least 710mAh/cm 2The volume that this means the active material in the electrode assemblie is high, thereby high discharge capacity is provided.The high volume of active material can obtain through controlling many variablees, and these variablees comprise ratio, the volume of cathode collector, the concentration of the active cathode material in the cathode mix and the volume of the separator in the electrode assemblie of interface input capacity and total input capacity.
With reference to figure 1, the present invention will be understood preferably, the figure illustrates a kind of embodiment according to battery of the present invention.Battery 10 is the cylindrical Li/FeS of a kind of FR6 type 2Battery.Battery 10 has shell, and it comprises the tube 12 with closed bottom and open top end, and said open top end is by battery cover 14 and packing ring 16 sealings.Near the top, tube 12 has crimping or subtracts the step of diameter, with supporting bead 16 and lid 14.Packing ring 16 is crushed on tube 12 and covers between 14, thus anode 18, negative electrode 20 and electrolyte in the sealed cell 10.Anode 18, negative electrode 20 and separator 26 are spirally wound on and become electrode assemblie together.Negative electrode 20 has metal collector 22, and it is connected to from top extension of electrode assemblie and by contact spring 24 and covers 14 inner surface.Through the metal tab (not shown), anode 18 is electrically connected to the inner surface of tube 12.Thereby the peripheral part at the top of insulator cone 46 surrounding electric poles assemblies prevents cathode collector 22 and 12 contact with tube, and the contact between the bottom of the bottom margin that prevents negative electrode 20 through inwardly folding extensions of separator 26 and the electric insulation chassis 44 in tube 12 bottoms and tins 12.Battery 10 has independently the anode utmost point (terminal) lid 40, its by tube 12 to crimped top and packing ring 16 fix in position.Tube 12 is as the negative contact jaw utmost point.Positive temperature coefficient (PTC) device 42 places between the peripheral flange and battery cover 14 of end polar cap 40, and its electric current that is substantially limited under the electrical conditions of abuse flows.Battery 10 also comprises the decompression exhaust hole.Battery cover 14 has the slit, and it comprises central row gas well 28 and the exhaust outlet 30 in well 28 bottoms that inwardly stretches out.This slit is deflated ball 32 and 34 sealings of thin-wall thermoplastic lining, and said lining 34 is crushed between the periphery of vertical wall and venting ball 32 of blast pit 28.When inner pressure of battery surpasses predeterminated level, venting ball 32, perhaps ball 32 and lining 34 both, be forced to leave the slit in case from battery 10 release pressurized gas.
Battery case is usually for having the metal cylinder of integrally closed bottom, yet also can use initial metal tube at both ends open to replace tube.This is steel normally, and coating (plate) has nickel to protect the outside of tube not corroded on outside at least.Can change the type of coating, thereby corrosion resistance in various degree is provided or the outward appearance of expectation is provided.Steel type will depend in part on the mode that forms container.For the tube of stretch (drawn), steel can be diffusion annealing steel, mild steel, aluminum killed steel, SAE 1006 or equivalent steel, wherein grain size be ASTM 9-11 and be wait axle to omiting the elongated grains shape.Also can use other steel such as stainless steel to satisfy specific (special) requirements.For example, when this tube contacts with cathodic electricity, can use stainless steel to improve resistance to the corrosion that causes by negative electrode and electrolyte.
Battery cover usually is a metal.Can use the nickel plating steel, but stainless steel usually is desired, particularly when this lid contacts with cathodic electricity.The complexity of lid shape also will be the factor that material is selected.Battery cover can have simple shape, and like thick square position, perhaps it can have more complicated shape, lid as shown in fig. 1.When lid had the complicated shape that is similar among Fig. 1,304 type soft annealing stainless steels with ASTM8-9 grain size can be used, thereby the corrosion resistance and the easy property of metal forming of expectation are provided.Formed lid also can be by coating, for example nickel plating.
The end polar cap should have the good resistance to the aqueous corrosion in the surrounding environment, good conductivity and property handsome in appearance (when being visible in consumption on battery).The end polar cap is usually processed by the cold-rolled steel of nickel plating or the steel of nickel plating after forming lid.When the end utmost point was positioned at top, decompression exhaust hole, the end polar cap had one or more mouthfuls usually so that the battery exhaust.
Packing ring is processed by the thermoplastic of any suitable sealing property that expectation is provided.Material selects part to form based on electrolyte.The instance of suitable material comprises polypropylene, polyphenylene sulfide, tetrafluoride perfluoroalkyl vinyl ether copolymer, polybutylene terephthalate (PBT) and its combination.Preferred gasket materials comprises polypropylene, and (for example, PRO- 6524 is available from Basell Polyolefins; Wilmington; DE, USA), polybutylene terephthalate (PBT) (
Figure G2009101331551D00102
PBT for example, 1600A level; Available from Ticona-US; Summit, NJ, USA) and polyphenylene sulfide (for example;
Figure G2009101331551D00103
PPS; Available from Boedeker Plasties, Inc., Shiner; TX, USA).Also can a spot of other polymer, reinforcing inorganic and/or organic compound be added in the base resin of packing ring.
Packing ring can be coated with sealant so that best sealing to be provided.Ethylene propylene diene rubber (EPDM) is suitable encapsulant, but the material that can use other to be fit to.
The exhaust lining is processed by thermoplastic, and this thermoplastic at high temperature (for example, 75 ℃) is cold-resistant stream.Thermoplastic comprises base resin such as ethylene-tetrafluoroethylene, polybutylene terephthalate (PBT), polyphenylene sulfide, polyphthalamide, ethene CTFE, CTFE, PFA, fluoridizes perfluoroethylene polypropylene and polyether-ether-ketone.Preferably ethylene-tetrafluoroethylene copolymer (ETFE), polyphenylene sulfide (PPS), polybutylene terephthalate (PBT) (PBT) and polyphthalamide.Can modified resin through adding the thermostabilization filler, thus the sealing and the discharge characteristic of the expectation under the high temperature are provided for the exhaust lining.Lining can be injection molded by thermoplastic.
Figure G2009101331551D00104
HT2004 (the ETFE resin contains 25wt% chopped glass fiber) is preferred thermoplastic.
Venting ball can be processed by any suitable material, and said material is stable when contacting with cell contents and the cell sealing and the discharge characteristic of expectation are provided.Can use glass or metal such as stainless steel.
Anode comprises the band of lithium metal, is sometimes referred to as the lithium paillon foil.The composition of lithium can be different, yet for the lithium of cell grade, purity is always high.Lithium can become alloy with other metal such as aluminium, thereby the cell electrical performance of expectation is provided.Cell grade lithium-the aluminium foil that contains 0.5wt% aluminium can be available from Chemetall Foote Corp., Kings Mountain, NC, USA.
Anode can lithium metal the surface in or on have current-collector.Like the battery among Fig. 1, possibly not need independently current-collector, because lithium has high conductivity, but can comprise current-collector, for example,,, in anode, keep electric continuity like this because lithium is consumed at interdischarge interval.When anode comprised current-collector, it can be made of copper (because its conductivity), but can use other conducting metal, as long as it is stable in battery.
Thin metal band is usually as electric lead, perhaps tab, and it is connected to anode on the battery-end utmost point (with regard to the FR6 battery shown in Fig. 1, be tin).Metal band is usually processed and directly is attached on the lithium by the steel of nickel or nickel plating.This can realize like this: the end of lead is embedded in the part of anode or simply the end of lead is pressed onto on the surface of lithium thin slice.
Negative electrode is a strips, and it comprises current-collector and contains the mixture that one or more are generally the electrochemical active material of particle shape.Ferrous disulfide (FeS 2) be preferred active material.At Li/FeS 2In the battery, active material comprises the FeS greater than 50wt% 2Negative electrode can also comprise one or more other active material, and this depends on the battery electrology characteristic and the flash-over characteristic of expectation.Other active cathode material can be any suitable activity cathode material.Instance comprises Bi 2O 3, C 2F, CF x, (CF) n, CoS 2, CuO, CuS, FeS, FeCuS 2, MnO 2, Pb 2Bi 2O 5And S.More preferably, be used for Li/FeS 2The active material of cell cathode comprises the FeS of 95wt% at least 2, more preferably, the FeS of 99wt% at least 2, most preferably, FeS 2Be unique active cathode material.Purity level is the LITHIUM BATTERY FeS of 95wt% at least 2Can be available from American Minerals, Inc., Camden, NJ, USA; Chemetall GmbH, Vienna, Austria; Washington Mills, North Grafton, MA; With Kyanite Mining Corp., Dillwyn, VA, USA.
Except active material, cathode mix comprises other material.Usually use adhesive microparticle material is fixed together and mixture is adhered on the current-collector.Thereby can add one or more electric conducting materials such as metal, graphite and hydrocarbon black powder and improved conductivity is provided to mixture.The quantity of used electric conducting material can depend on factors such as thickness and the current-collector design of conductivity like active material and adhesive, the mixture on the current-collector.Also can use a spot of various additive to strengthen negative electrode manufacturing and battery performance.Below be to be used for Li/FeS 2The instance of the active material mixture material of cell cathode.Graphite: KS-6 and
Figure G2009101331551D00121
MX15 level Delanium; Available from TimcalAmerica; Westlake; OH, USA.Carbon black: C55 level acetylene black, available from Chevron PhillipsCompany LP, Houston, TX, USA.Adhesive: ethylene/propene copolymer (PEPP), (preceding Polysar Inc.) makes and can be available from HarwickStandard Distribution Corp., Akron, OH, USA by Polymont Plasties Corp.; Non-ionic water-soluble polyethylene glycol oxide (PEO): is available from Dow Chemical Company; Midland; MI, USA; With G1651 level styrene-ethylene/butylene-styrene (SEBS) block copolymer, available from KratonPolymers, Houston, TX.Additive: FLUO
Figure G2009101331551D00123
micronizing polytetrafluoroethylene (PTFE); By Micro Powders Inc.; Tarrytown, NY, USA makes (can be commercially available available from Dar-TechInc.; Cleveland; OH is USA) with
Figure G2009101331551D00124
200 grades of fumed silicas, available from Degussa Corporation Pigment Group; Ridgefield, NJ.
Current-collector can be placed in the cathode surface or embed in the cathode surface, and perhaps cathode mix can be applied on the one or both sides of thin metal band.Aluminium is normally used material.Current-collector can extend beyond the cathode portion that contains cathode mix.This extension of current-collector can provide the suitable electric lead contact of area to be connected with the anode utmost point.The volume that is desirable to the extension of current-collector is retained to minimum value, makes that the active material and the obtainable battery inner volume of electrolyte that make are big as far as possible.
Make FeS 2The method for optimizing of negative electrode is that the slurries with the active material mixture material in the volatile organic solvent (for example trichloroethylene) are rolled onto on the both sides of aluminium foil; Dry coating desolvates to remove; The paillon foil that is coated of calendering is with the densification coating, the width and the cutting of the paillon foil rip cutting (slit) that is coated to expectation brought to expectation by the bar of the cathode material of rip cutting length.Be desirable to use and have the cathode material of low particle size so that minimize the risk that pierces through separator.For example, before the use, preferably with FeS 2Screening is through the screen cloth of 230 orders (63 μ m).
In further embodiment, a kind of negative electrode or anodal is disclosed, it is to having combined said negative electrode or anodal electrochemical cell that useful performance is provided.Negative electrode comprises the FeS with predetermined average particle size particle size 2Particle, said particle is produced through wet grinding method such as medium milling or dry grinding method (using on-mechanical lapping device such as jet mill).By the average particle size particle size FeS that reduces 2The electrochemical cell of granulate preparation demonstrates the cell voltage that under the condition of any given depth of discharge, increases, no matter battery sizes how.
In one embodiment of the invention, negative electrode comprises low particle size FeS 2Particle, preferred natural, produce by the wet grinding method, preferably utilize medium grinder.Medium grinder also is called ball mill, basket grinding machine (basket mill), ball mill (bead mill), sand mill, rotating cylinder blender etc. in the art, and it can use abrasive media in the wet grinding method.The wet grinding step is preferably vertically carried out between negative electrode or anodal tectonic epochs, eliminates weathering or oxidation and harmful dry dust pyrite catch fire (fire) thus basically.Through utilizing wet grinding method of the present invention, can remove above-mentioned screening operation from.
In the wet grinding method, form electrochemical cathode active material mixture, comprise FeS 2And wetting agent.At this moment in the method, FeS 2Average particle size particle size greater than 20 μ m.If expectation can also use any above-mentioned activity or passivity material such as, but be not limited to adhesive, electric conducting material, additive etc. in the active material mixture.In one embodiment, the active material of cathode component of mixture is merged, and randomly, but preferably, mix in suitable containers.The cathode active material material mixture is metered in the medium grinder, wherein FeS during grinding 2The average particle size particle size of particle reduces.The residence time of cathode active material material mixture is enough to produce the FeS with expectation average particle size particle size in medium grinder 2
Wetting agent is any liquid etc., and preferably low viscous, it prevents FeS basically 2Perhaps other component of slurries is burnt in process of lapping.Preferred humectants is a solvent, and it is non-flammable in wet grinding operating period under used processing conditions usually.The instance of suitable wetting agent includes, but are not limited to trichloroethylene, N-N-methyl-2-2-pyrrolidone N-(NMP), butyl glycol acetate, rosin (mineral spirits) and water.Select wetting agent with adhesive fit used at least and in the negative electrode preparation and preferably can dissolve this adhesive basically.The quantity of wetting agent can change, and can be generally the solid constituent of every gram cathode active material material mixture, and the about 5cc of about 0.1cc-preferably, is about 0.5cc.
The active material of cathode slurry mixture is transferred to lapping device and under suitable flow rate and rotor rpm, grinds, up to the FeS that obtains expectation 2Average particle size particle size.Working medium grinder in preferred embodiments.Medium grinder usually comprises rotating disk and/or the rotor and the abrasive media of axle assembling, so that reduce the particle size of the component of composition to be ground.It is spherical, cylindrical that abrasive media can be essentially or the like, and sphere is preferred, and average diameter is the about 30mm of about 0.2mm-, the about 10mm of about ideally 0.5-, the about 1.7mm of preferably about 1.2-.The cylinder height is the about 20mm of about 1mm-, and the about 15mm of wherein about 5-is preferred.The medium of many types can be used, including, but not limited to the zirconium dioxide and the tungsten carbide of the stable zirconium dioxide of zirconium dioxide silicon dioxide, chromium steel, zirconium silicate, the cerium of soda lime, zirconia-silicon dioxide, aluminium oxide, stabilized with yttrium oxide, stabilized with yttrium oxide.Suitable abrasive media can be available from supplier such as Saint-Gobain ofWorcester, MA (trade name Glass, ERl 20, Zirstar and Zirmil); Glenn Mill ofCliffton, NJ (trade name Alumina, Steel and Carbide); With Jyoti CeramicIndustries of Satpur, Nashik, India (trade name Zirconox and Zircosil).Suitable medium grinder can be available from Morehouse-COWLES of Fullerton, California.
The active material of cathode slurry mixture is transferred to the grinding chamber of medium grinder, and said medium grinder comprises the rotatable rotor of abrasive media and preferred earth's axis assembling.Medium quickens to march on towards the grinding chamber locular wall through slurries at a relatively high speed, impacts, shears the slurry mixture particle thus and make its size decreases.FeS in the average particle size particle size that obtains expectation 2Behind the particle, subsequently the slurry mixture that grinds is discharged from medium grinder, so that be processed into negative electrode further.
After utilizing wet grinding method processing of the present invention, FeS 2The average particle size particle size of particle is the about 19 μ m of about 1-, about ideally 2-about 17 or about 18 μ m, preferably, about 5 or the about 15 μ m of about 10-.Since the medium milling method of carrying out above that, FeS 2Particle also has narrower particle size distribution.
The active cathode material mixture of wet grinding subsequently roller coat on sheet material such as aluminium foil, as indicated above, and be dried to remove wetting agent.The foil laminate that is coated then can be by calendering so that coating densification and produce smooth surface, the paillon foil that is coated can be used for electrochemical cell assembly by rip cutting to the width and the length of expectation, described in this paper.
In the further embodiment of the present invention, negative electrode comprises having by the on-mechanical lapping device, preferably the FeS of the predetermined average particle size particle size of jet mill acquisition 2Particle, preferred natural.Term " on-mechanical lapping device " is meant a kind of device, and it does not utilize pressure or contact between two or more lapped faces that the particle size of material is reduced, as through pulverizing, smear metal, fracture etc.Mechanical lapping equipment is including, but not limited to rolling grinding machine, granulation grinder, ball mill, medium grinder, ball mill and hammer-mill.The on-mechanical lapping device does not usually use mobile grinding component to reduce FeS 2The average particle size particle size of particle utilizes the collision between the single surface of particle and/or particle and grinder device to reduce size on the contrary.
Jet mill usually comprises central lumen, and fluid such as air, steam or gas are introduced in the central lumen through nozzle (nozzles) or jet pipe (jets), and this nozzle or jet pipe produce near-sonic speed, velocity of sound or supersonic grinding logistics.Do not use abrasive media.Contain FeS 2The feed material particle of particle is ground in the logistics by the high speed that charging perhaps is injected in the jet mill.Since the high velocity impact between the particle of ferrous disulfide or other particle itself perhaps with the collision of lapped face, make size reduce.The jet mill purpose is to make excessive particle recirculation, the generation and the effect of reinforcing particle collision.Along with FeS 2Particle size reduces, and they move towards discharging opening, collects them to be used to form the used active material mixture of negative electrode at discharging opening.In a kind of embodiment preferred, in the inert atmosphere that utilizes gas such as nitrogen, argon gas etc. (nitrogen is most preferred), carry out FeS 2Jet grinding, in order to avoid FeS 2Particle is lighted or is burnt.Though through the FeS that on lapped face, rubs 2Friction of granule effect or the collision that in grinder, takes place can produce heat, and at least owing to the Jewel-Thompson effect of air themperature when throttling, it is reported does not have clean temperature to raise during grinding.Product temperature is substantially equal to offer the temperature of the fluid of grinder.Jet mill can available from Jet Pulverizer Company (Moorestown, NJ); Sturtevant (Hanover, MA); And Fluid Energy (Telford, PA).
After utilizing the processing of on-mechanical of the present invention or jet grinding method, FeS 2The average particle size particle size of particle is for being the about 19 μ m of about 1-, about ideally 1.5-about 10 or about 15 μ m, the about 6 μ m of preferably about 2-.The FeS of jet grinding 2Particle has such particle size distribution, and wherein 80% of whole particles is the about 15 μ m of about 1.0-, the about 10 μ m of preferably about 1.0-.Use foregoing Microtrac Honeywell grain size analysis appearance X-100 to confirm particle size distribution, wherein use sonicated in order to avoid particle aggregation at test period.
In scope as herein described, reduce FeS 2The used Ginding process of the present invention of the average particle size particle size of particle has demonstrated some advantages; This for example comprises; Improved low temperature battery performance; The adhesion of improved cathode active material material mixture and aluminium base; To polymer spacer insulator film minor harm (because active material mixture low particle size), improved cathode efficiency (because the pyrite particle of surface area that more has an increase is to accept lithium ion when the battery discharge), improved battery operated voltage (comes from the anode polarization of reduction; This make battery for the firm power device is used with lower current work) and more efficient with equably discharge on the relative lithium anode (because CURRENT DISTRIBUTION can be applied on its interfacial surface area more equably).
When lying prostrate, utilize the FeS of wet grinding with the continuous discharge to 1 of 200mA speed 2The FeS of particle or jet grinding 2The FR6 type electrochemical cell of granulate preparation can provide the discharge capacity of at least 3,000 milliampere-hour (mAh), and when at room temperature with 1 ampere of speed continuous discharge to 1 volt, 2700mAh or preferably at least 2 at least, 800mAh.Therefore, battery of the present invention provides fabulous result for low the application with high load capacity.
Also found to use FeS like disclosed jet grinding in the present invention 2The discharge time of the FR6 electrochemical cell of particle, (to 1.05 volts) were generally at least 300 minutes; At least 320 minutes ideally; Preferably at least 325 minutes and most preferably at least 330 or 340 minutes, test according to 2/28 second * 10/ hour DSC of 1500/650mW.Also found to contain the FeS of the jet grinding of the average particle size particle size in the scope with defined among the present invention 2The FR6 type electrochemical cell of particle is kept voltage and is reached at least 180 minutes more than or equal to 1.2 (volts), at least 240 minutes ideally, preferably at least 270 minutes, tests according to 2/28 second * 10/ hour DSC of 1500/650mW.The DSC method utilizes two pulses to make the electrochemical cell periodic duty, and first pulse reaches 2 seconds at 1500mW, and second pulse subsequently reaches 28 seconds at 650mW.Pulse train repeats 10 times, is 55 minutes time of having a rest subsequently.Then, repetition pulse sequence and time of having a rest are to predetermined voltage.In addition, also find to contain the FeS of wet grinding 2The FR6 type electrochemical cell of particle keeps reaching at least 180 minutes more than or equal to the voltage of 1.2 (volts), at least 210 minutes ideally, preferably at least 230 minutes, tests according to 2/28 second * 10/ hour DSC of 1500/650mW.Utilize the FeS of wet grinding 2The FR6 type electrochemical cell of particle has at least 300 minutes usually, discharge time of at least 320 minutes (to 1.05 volts) preferably, tests according to 2/28 second * 10/ hour DSC of 1500/650mW.Measure and at room temperature carry out.
Like what Fig. 5 set forth, when with contain average-size more than or equal to about 22 microns FeS 2When the prior art battery of particle is compared, be used to come from the less average particle size particle size FeS of Ginding process of the present invention such as wet method or jet grinding 2The FR6 electrochemical cell of granulate preparation provides the anode voltage value that reduces under different depth of discharges.Under 50% depth of discharge, has the FeS of the average particle size particle size in the scope of the invention 2The anode voltage of the electrochemical cell of particle is less than 190 millivolts, ideally less than 170 millivolts, preferably less than 100 millivolts, most preferably less than about 60 millivolts.Under 25% depth of discharge, anode voltage is less than 140 millivolts, ideally less than 120 millivolts, preferably less than 75 millivolts.In order to obtain measurement result, use Solartron 1470 (can be available from Solartron Analytical, Farnborough England) makes battery discharge.Select electric current to make current density be about 5mA/cm 2Make the battery periodic duty, 1 ampere of work was worked 5 minutes in 2 minutes and 0 ampere.Reference battery is to obtain like this: remove the battery tube bottom; And this battery is suspended in contains in the electrolytical beaker; In this case, electrolyte is 1,3-dioxolanes, 1; 2-diethoxyethane and 3,5-dimethyl isoxazole (63.1: 27.6: the lithium iodide (lithium iodine) of the every liter of solvent 0.75mol (9.1wt%) in solvent blend 0.20wt%).Reference electrode is the pure metal lithium band in having the most advanced and sophisticated syringe bucket of quartz glass (Vycor), and it is in battery side and breaks off.Before discharge, made this system balancing about 30 minutes.Measure and at room temperature carry out.
Cathodic electricity is connected to the anode utmost point of battery.As shown in Figure 1, this can realize that form usually is metal band or the spring that approaches with electric lead.This lead is usually processed by the stainless steel of nickel plating.
Separator is the microporous barrier that approaches, its be ion-permeable and be electric insulation.It can be contained at least some electrolyte in the hole of separator.Separator is placed between the adjacently situated surfaces of anode and negative electrode so that electrode is electrically insulated from each other.The part of separator also can make other element insulating that electrically contacts with the battery-end utmost point to prevent internal short-circuit.The edge that the edge of separator usually extends beyond at least one electrode does not electrically contact to guarantee anode and negative electrode, even they are not aimed between having mutually fully.Yet, be desirable to the amount that minimizes the separator that extends beyond electrode.
For good high power discharge performance is provided; Desired is that separator has like United States Patent (USP) 5; 290; (in the porosity of 30-70%, hole has the minimum dimension of at least 0.005 μ m and the full-size of 5 μ m at the most to disclosed characteristic in 414 (mandates on March 1st, 1994), and area is 2-15ohm-cm than resistance 2With curvature less than 2.5), this patent is introduced this paper as a reference.Suitable spacer material also should be enough firm in to stand battery manufacturing process and possibly not have to cause crack, otch, the leak of internal short-circuit or other breach that forms putting on the pressure on the separator during the battery discharge.
Be the total separator volume in the minimise battery, separator should be thin as far as possible, but at least about 1 μ m or bigger, make between negative electrode and anode, to exist physical obstacle to prevent internal short-circuit.That is to say that the thickness of separator is the about 50 μ m of about 1-, the about 25 μ m of about ideally 5-, preferably about 10-about 16 or about 20 μ m.Size and position that desired thickness will depend in part on the intensity of spacer material and possibly put on the power on the separator (wherein it provides electric insulation).
Except that thickness, numerous characteristics also can influence separator intensity.One in these is tensile stress.High tensile stress is desired, preferably at least 800, and at least 1000 kilograms/square centimeter (kgf/cm more preferably 2).Because manufacturing process is usually used for making the microporosity separator, the tensile stress in vertically (MD) is usually greater than the horizontal tensile stress of (TD).Required minimum stretch stress possibly depend in part on the diameter of battery.For example, for FR6 type battery, preferred tensile stress vertically goes up and is 1500kgf/cm at least 2, 1200kgf/cm at least transversely 2, the preferred tensile strength of vertical and horizontal is respectively 1300 and 1000kgf/cm for FR03 type battery 2If tensile stress is too low, manufacturing and internal cell power possibly cause tears or other hole.Usually, tensile stress is high more, and is good more from the intensity angle.Yet if tensile stress is too high, the desired performance of other of separator possibly be adversely affected.
Tensile stress can also represent that it can be by tensile stress (kgf/cm with kgf/cm 2) calculate, method is the thickness (cm) that multiply by separator with the latter.The tensile stress that with kgf/cm is unit also can be used for finding the desired performance relevant with separator intensity.Therefore, the tensile stress of desired is separator is 1.0kgf/cm at least in vertical and horizontal, 1.5kgf/cm at least preferably, more preferably 1.75kgf/cm at least.For the battery of diameter greater than about 0.45 inch (11.4mm), most preferably tensile stress is 2.0kgf/cm at least.
Another index of separator intensity is its dielectric breakdown voltage.Preferably, average dielectric breakdown voltage will be at least 2000 volts, more preferably at least 2200 volts.For the cylindrical battery of diameter greater than about 0.45 inch (11.4mm), average dielectric breakdown voltage most preferably is at least 2400 volts.If dielectric breakdown voltage is too low, be difficult to during the battery manufacturing, remove battery (for example, adding the high-tension retention rate that electrolyte was applied to electrode assemblie in the past) reliably with the separator that lacks or damage through electrical check.Desired is when still obtaining other desired separator performance, the dielectric breakdown value as far as possible greatly.
The average effective aperture is another prior separator intensity index.Ion is carried through the separator maximization though macrovoid is desired, if hole is too big, separator will be responsive to infiltration and interelectrode short circuit.Preferred maximum effective aperture is 0.08 μ m-0.40 μ m, more preferably is not more than 0.20 μ m.
The BET specific area is also relevant with pore size and hole count.Usually, when separator had high specific surface area, cell discharge performance was better often, but separator intensity is lower often.For the BET specific area desired be to be not more than 40m 2/ g expects that also it is 15m at least 2/ g more preferably is at least 25m 2/ g.
For good high load capacity and high power battery discharge performance, low area is desired than resistance.Thin separator often has lower resistance, but separator also should be enough firm, and this has limited the possible thinness of separator.Preferably, area is not more than 4.3ohm-cm than resistance 2, more preferably be not more than 4.0ohm-cm 2, most preferably be not more than 3.5ohm-cm 2
The separator film that is used for lithium battery is usually become by polypropylene, polyethylene or ultrahigh molecular weight polyethylene, preferably polyethylene.Separator can be the microporous barrier of one deck biaxial orientation, perhaps can with two-layer or more laminated multi-layer together so that the hot strength of expectation to be provided in orthogonal direction.Preferred single layer is to minimize cost.The polyethylene micropore property separator of suitable individual layer biaxial orientation can be available from Tonen Chemical Corp., can be available from EXXON Mobile Chemical Co., Macedonia, NY, USA.Setela F20DHI fire resisting division thing has the nominal thickness of 20 μ m, and Setela 16MMS level has the nominal thickness of 16 μ m.
Anode, negative electrode and separator band combine in electrode assemblie.Electrode assemblie can twine design for spiral, and as shown in fig. 1, it is processed like this: around mandrel the alternately band of negative electrode, separator, anode and separator is twined, when winding is accomplished, from electrode assemblie, take out mandrel.Usually around the outside of electrode assemblie, wrap up one deck separator and/or one deck electric insulating film (for example polypropylene) at least at least.This plays multiple effect: it helps assembly is fixed together, and can be used to the width or the diameter of assembly are adjusted to desired size.The outermost end of separator or other outer film layer can be used adhesive tape or fix through heat seal.
Be different from spiral and twine, electrode assemblie can form through electrode and separator band are folded.Band can be along its length direction alignment; Folding with Zhe shape form then; Perhaps anode and an electrode band can be laid perpendicular to negative electrode and another electrode band; One at electrode is striden another alternate folding (vertical orientated), under two kinds of situation, forms the anode alternately and the lamination of cathode layer.
Electrode assemblie is inserted in the outer casing container.With regard to the electrode assemblie that spiral twines, no matter be in cylindrical or prismatic container, the main Surface Vertical of electrode is in the sidewall (in other words, the central core of electrode assemblie is parallel to the longitudinal axis of battery) of container.Folding electrode assemblie is usually used in the prismatic battery.With regard to the folding electrode assemblie of Zhe shape; The orientation of this assembly is such; Make smooth electrode surface be adjacent to the opposite side of container in the opposite two ends of the lamination of electrode layer; In these configurations, the gross area on the main surface of most anode adjoins the gross area on the main surface of most negative electrode through separator, and the outermost portion on the main surface of electrode is adjacent to the sidewall of container.Like this, because the expansion of the electrode assemblie that the increase of the gross thickness of anode and negative electrode causes will receive the restriction of container side wall.
Nonaqueous electrolyte, the water that only contains minute quantity is used in the battery of the present invention as impurity (for example about at the most 500ppm by weight, depends on used electrolytic salt).Can use and be suitable for any nonaqueous electrolyte of using with lithium and active cathode material.Electrolyte comprises one or more electrolytic salts that is dissolved in organic solvent.For Li/FeS 2Battery, the instance of suitable salt comprise lithium bromide, lithium perchlorate, lithium hexafluoro phosphate, Potassium Hexafluorophosphate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium and lithium iodide; Appropriate organic solvent comprises one or more in following: dimethyl carbonate, diethyl carbonate, carbonic acid Methylethyl ester, ethylene carbonate, propylene carbonate, carbonic acid 1; 2-fourth diester, carbonic acid 2; 3-fourth diester, methyl formate, gamma-butyrolacton, sulfolane, acetonitrile, 3; 5-dimethyl isoxazole, N, dinethylformamide and ether.Salt/solvent bond will provide enough electrolysis and conductivity in desired temperature range, to satisfy the battery discharge requirement.Ether usually is desired, because they are normally low viscous, have good wet volume capacity, good low temperature performance and good high load capacity discharge performance.At Li/FeS 2Especially true in the battery, than having MnO 2Negative electrode, ether are more stable, so can use higher ether level.Suitable ether includes, but are not limited to acyclic ether as 1,2-dimethoxy-ethane, 1,2-diethoxyethane, two (methoxy ethyl) ether, triglyme, tetraethylene glycol dimethyl ether and ether; With cyclic ethers as 1,3-dioxolanes, oxolane, 2-methyltetrahydrofuran and 3-methyl-2-oxazolidone (oxazolidinone).
Therefore, the various combinations that can use electrolytic salt and organic solvent are to be formed for the electrolyte of electrochemical cell.The molar concentration of electrolytic salt can change to change electrolytical electric conductivity.The suitable instance that contains one or more nonaqueous electrolytes that are dissolved in the electrolytic salt in the organic solvent including, but not limited to 1 moles per litre of solvent concentration 1; 3-dioxolanes, 1; 2-diethoxyethane and 3; The 5-dimethyl isoxazole (24.80: 60.40: the 0.20wt%) trifluoromethyl sulfonic acid lithium in the solvent blend (14.60wt%), its conductivity is 2.5mS/cm; 1.5 moles per litre of solvent concentration 1,3-dioxolanes, 1,2-diethoxyethane and 3, the 5-dimethyl isoxazole (23.10: 56.30: the 0.20wt%) trifluoromethyl sulfonic acid lithium in the solvent blend (20.40wt%), its conductivity is 3.46mS/cm; With 0.75 moles per litre of solvent concentration 1,3-dioxolanes, 1,2-diethoxyethane and 3, (63.10: 27.60: the 0.20wt%) lithium iodide in the solvent mixture (9.10wt%), its conductivity was 7.02mS/cm to the 5-dimethyl isoxazole.Electrolytical conductivity used in electrochemical cell of the present invention is usually greater than about 2.0mS/cm, ideally greater than about 2.5 or about 3.0mS/cm, is preferably more than about 4, about 6 perhaps about 7mS/cm.
Can adjust concrete anode, negative electrode and electrolytical composition and quantity so that battery manufacturing, performance and the storage characteristics of expectation to be provided.
Can use any suitable technology to come closed and sealed battery.These technologies can be including, but not limited to curling, stretching (redrawing) again, fitted tube folder (colleting) and its combination.For example,, after inserting electrode and insulator cone, in tube, form crimping, packing ring and cap assemblies are placed (comprising battery cover, contact spring and exhaust lining) this openend for the battery among Fig. 1.Cell support on crimping, is pushed away packing ring and cap assemblies downwards against crimping simultaneously.The top diameter of the tube more than crimping reduces so that packing ring and cap assemblies are fixed on the appropriate location in the battery along with fan-shaped collet chuck.After being assigned in battery through the aperture in exhaust lining and the lid electrolyte, venting ball is inserted in this lining in battery cover, to make the aperture sealing.Above battery cover, PTC device and end polar cap are placed on the battery, by the mould that curls the top of tube is curved inwardly holding retention washer, cap assemblies, PTC device and end polar cap, and accomplish the sealing of the openend of tube through packing ring.
Foregoing description relates in particular to cylindrical Li/FeS 2Battery is like FR6 and FR03 type, as defined among International Standards IEC 60086-1 and the IEC 60086-2 (being published Geneva, Switzerland by InternationalElectrotechnical Commission).Yet, the battery that the present invention also can be adapted to other battery size and shape and have other electrode assemblie, shell, sealing and the design of decompression exhaust hole.
In following examples, will set forth characteristic of the present invention and its advantage further, wherein unless otherwise mentioned, at room temperature make an experiment.
Embodiment 1
The cylindrical Li/FeS of FR6 type with spiral winding electrode assemblie 2Battery is with at the about 0.455cm of about 0.373- 3The electrode assemblie voidage of the every centimetre of different interface electrode assemblie height the in/cm scope is processed.Volume through being adjusted at the space in the active material mixture that is coated on the negative electrode changes voidage.These various combinations through design of mixture, thickness and assembling are accomplished.The spacer material that is used for all batteries is the capillary polypropylene material of high crystalline state, uniaxial orientation, has 25 μ m nominal thickness.
Embodiment 2
The sample of the battery of preparation embodiment 1 is in order to test.For each group of the voidage with given per unit height, some batteries keep discharge, and some battery discharges 50% (reaching required time to remove 50% rated capacity with the discharge of 200mA speed).Discharge is not carried out the test of relevant shock-testing with 50% discharge battery, at test period and test the ambient temperature of monitoring each battery of being tested in back 6 hours.
For shock-testing, the sample battery is placed on the flat surface, the bar of diameter 15.8mm is striden the sample center place, from highly being that 61 ± 2.5cm falls the object of 9.1kg to sample.The sample battery is impacted, and its longitudinal axis is parallel to flat surface, perpendicular to the longitudinal axis across the bar of the diameter 15.8mm at battery center.Each sample only receives one-shot.
The ambient temperature of the battery of discharge does not all have above 170 ℃.The percentage of 50% discharge battery of temperature above 170 ℃ is mapped to external world.The best curve of match original plotting point is shown among Fig. 2, the voidage of its per unit height (cm of unit 3/ cm) at the x axle, and the percentage of the battery of ambient temperature above 170 ℃ is at the y axle.
Shock-testing is the result show, when the electrode assemblie voidage reduced, the percentage with battery of the ambient temperature that surpasses 170 ℃ raise.By the curve among Fig. 2, with the 0.45cm that voidage is about interfacial level that has of prediction 0% 3The battery of/cm will have the ambient temperature above 170 ℃, and predict that the voidage above 60% is approximately 0.37cm 3/ cm's will be above 170 ℃.High ambient temperature is owing to the infringement of separator, and this causes producing the internal short-circuit of heat.
Two FR6 Li/FeS behind different discharge levels 2The check subsequently of battery shows, during battery discharge 50%, the net increase of the electrode volume that the FR6 battery is total (its carry out along with discharge and become bigger) causes the bending of electrode band and the prostheses of warpage and flattening electrode assemblie.On the contrary, has the Li/MnO that spiral twines electrode 2The similar check of battery has shown that electrode assemblie does not almost have recognizable variation when 50% discharge.Difference between the volume of active material volume and exoelectrical reaction product has been explained at Li/FeS 2Than Li/MnO 2The spiral of battery twines the difference of the discharge effect on the electrode assemblie.
Embodiment 3
Made four batches of FR6 batteries, every batch has the separator that is made from a variety of materials.The description of spacer material is provided in the table 1, and typical separator performance as being confirmed by the method that is described below, is summarized in the table 2.Batch spacer material that A is used is identical with the material of the battery that is used for embodiment 1.Each battery comprises the electrolyte of about 1.60g, and this electrolyte is by 1,3-dioxolanes, 1, and 2-dimethoxy-ethane and 3, the 5-dimethyl isoxazole (63.05: 27.63: 0.18, formed by the LiI salt of the 9.14wt% in the solvent blend by weight).Table 1
Batch A Batch B Batch C Batch D
The capillary polypropylene of high crystalline state uniaxial orientation, 25 μ m are thick The capillary polypropylene of high crystalline state uniaxial orientation, 20 μ m are thick The micropore ultra-high molecular weight polyethylene of amorphous state biaxial orientation, 20 μ m are thick The microporous polyethylene of amorphous state biaxial orientation, 20 μ m are thick
For whole batches of A-D, use identical battery design.This battery design is that a kind of battery than embodiment 1 (its electrode assemblie voidage is about 0.452 with the ratio of interfacial level) has more substantial active material, in cathode mix, has the FeS of higher concentration 2And have higher electrode interface surface area and have lower anode: the design of the total input capacity ratio of negative electrode causes battery interface capacity to increase by 22%.
Embodiment 4
Make the battery discharge 50% of each batch among the embodiment 3, carry out the test of relevant shock-testing then.For a batch A, the percentage that surpasses 170 ℃ battery in this test is 20%, is 80% for batch B, is 0% for batch C and D.
Than the battery (its electrode assemblie voidage is about 0.452 with the ratio of interfacial level) of embodiment 1, through improving interface capacity 22%, the percentage that surpasses 170 ℃ battery in this shock-testing brings up to 20% from 0%.The voidage that the battery of batch A has a decrease is with the net increase of the volume that holds (than the volume of unreacted active material) exoelectrical reaction product, and this has increased viewed Li/FeS among the embodiment 2 2The reaction of the discharge of electrode assemblie.
Than a batch A, the percentage that the thickness of the spacer material that reduces among batch B helps in shock-testing, to surpass 170 ℃ battery further is increased to 80% from 20%.
Although the thickness of the spacer material among batch C and the D is identical with batch thickness of B separator, in batch C or batch D, there is not battery.Although voidage in the negative electrode and spacer material thickness have all reduced in batch C and D, the result of batch C and D can compare with the battery (its electrode assemblie voidage is about 0.452 with the ratio of interfacial level) of embodiment 1.
Embodiment 5
In than underload and higher load discharge test, the actual performance of using three batches FR6 battery to come comparison FR6 battery.First batch is batch D of embodiment 3.The characteristic of batch D is summarized in the table 3.Listed numerical value is nominal value and possibly in typical manufacturing tolerance, changes.
Make the battery among batch E and the F according to prior art.Battery among batch F is similar to those (its electrode assemblie voidage is about 0.452 with the ratio of interfacial level) among the embodiment 1.The characteristic of batch E and F is shown in Table 3.In batch E, use with batch F in identical spacer material, but in batch E, changed the cathode mix composition and than a batch F, battery interface capacity has increased by 18%.In batch D, use thin separator (20 μ m are thick) to make and increased by 22% than a batch F battery interface capacity.Table 3
Figure G2009101331551D00241
Embodiment 6
The battery of each among batch D, E and the F under 200mA continuous discharge to 1.0 volt and under 1000mA continuous discharge to 1.0 volt.Table 4 has compared the result.Table 4
Test Batch D Batch E Batch F
200mA 3040mAh 2890mAh 2417mAh
1000mA 2816mAh 2170mAh 2170mAh
Confirm following spacer material performance according to correlation method.Unless otherwise mentioned, whole disclosed performances at room temperature (20-25 ℃) confirm.Tensile stress according to ASTM D882-02, uses Instron 1123 type UniversalTester to confirm.Sample is cut into 0.50 inch (1.27 centimetres) * 1.75 inches (4.45 centimetres).Initial length between vices be 1 inch (2.54 centimetres) and strain rate be 2 inches (5.08 centimetres)/minute.Calculate tensile stress according to applied force divided by initial area of section (width perpendicular to the sample of applied force multiply by sample thickness).Maximum effective aperture, it is to measure on the image that obtains down in 30,000 times of amplifications of use scanning electron microscopy and cover 4 μ m * 3 μ m zone.For each separator sample, image is formed by two main surfaces.On each image, measure maximum pore to confirm maximum round diameter, it is (maximum effective diameter of single hole) in the scope of hole wall.(that is the mean value of four single holes) is calculated through the maximum effective aperture of two maximum pore on average each side in the maximum effective aperture of sample.Porosity, it is confirmed as follows: the sample of (1) cutting separator, (2) weighing sample; (3) length of measuring samples, width and thickness; (3) from weight and measured value bulk density, (4) are with the solid density of bulk density divided by the separator polymer resin, like what provided by separator manufacturer; (5) dividend (dividend) multiply by 100 and (5) from this value, deduct 100.Dielectric breakdown voltage; It is to confirm like this: the separator sample is placed between two stainless steel pins; Each pin diameter is 2 centimetres and has the discoid tip; Use QuadtechModel Sentry 20 flash test devices (hipot tester), apply the voltage of raising at the pin two ends, and write down the voltage (voltage during the arc-through sample) that is shown.Tensile elongation (elongation at break), it uses Instron1123 type universal testing machine to confirm according to ASTM D882-02.Sample is cut into 0.50 inch (1.27 centimetres) * 1.75 inches (4.45 centimetres).Initial length between vices be 1 inch (2.54 centimetres) and strain rate be 2 inches (5.08 centimetres)/minute.Tensile elongation is to calculate like this: sample length deducts initial sample length during fracture, and both differences multiply by 100% divided by initial sample length and dividend.Area is than resistance (ASR), for the separator sample in the electrolyte that is suspended between two platinum electrodes, use 34 type electricity lead-ohmer (available from Yellow Springs Instrument, YellowSprings, OH USA) carries out resistance measurement to confirm this value.Used electrolyte solution is 1,3-dioxolanes, 1, and 2-dimethoxy-ethane and 3, the 5-dimethyl isoxazole (63.05: 27.63: 0.18, the 9.14wt%LiI salt in the solvent mixture by weight).In less than the water of 1ppm and atmosphere, all test less than the oxygen of 100ppm.The electric insulation sample holder is used for clamping separator sample, and wherein area is 1.77cm 2Separator be exposed, this clamper is immersed electrolyte solution, make the part of clamper clamped sample be positioned at interval the middle of 0.259 centimetre two platinum electrodes.Resistance between measurement electrode.From electrolyte, take out clamper, the separator sample is inserted in the clamper, clamper is slowly put into electrolyte solution to the identical level that is provided with, make sample be full of electrolyte fully and entrained bubbles not in sample.Measuring resistance.Use computes ASR:ASR=A (R 2-R 1+ ρ L/A) wherein A is the area of the separator sample that is exposed, R 2Be the resistance value when having film, R 1Resistance value when being no film, L is that separator thickness of sample and ρ are used electrolytical conductivity.Specific area, and use TriStar gas absorption analyzer (available from MicromeriticsInstrument Corporation, Norcross, GA USA) confirms through the BET method.The sample of the separator of 0.1g-0.2g is cut into less than 1cm 2Fragment with the accommodate sample clamper, under nitrogen stream, made the sample degassing 1 hour at 70 ℃, use nitrogen as adsorbent gas and collect complete adsorption/desorption thermoisopleth and carry out the pore-size distribution analysis.
Embodiment 7
Cylindrical FR6 type lithium/FeS with spiral winding electrode assemblie 2Battery is by different average particle size particle size FeS 2Particle is processed: the coarse granule size FeS of 22 μ m (contrast), 75 μ m 2, 5-10 μ m the FeS of medium milling 2The FeS of the jet grinding of (calculating valuation) and 4.9 μ m 2Except FeS 2Outside the technique change of average particle size particle size and typical and expection, battery is identical with the battery of batch D of table 3.Fig. 3 a and 3b respectively by the cathode slurry mixture of conventional (grinding) and medium milling process the SEM photo of cross section of negative electrode of coating.
2/28 second * 10/ hour DSC tests the discharge time of each battery to use 1500/650mW mentioned above.The result is shown among table 5a and the 5b.Use contains the FeS of medium milling 2Battery carry out two groups of tests.Table 5a
Figure G2009101331551D00271
table 5b
Operation FEP Contrast 22 μ m Medium milling 5-10 μ m Improve Contrast 22 μ m Medium milling 5-10 μ m Improve
1.2V 188 minutes 236 minutes 1.25 184 minutes 230 minutes 1.25
1.1V 281 minutes 311 minutes 1.11 277 minutes 304 minutes 1.10
1.05V 305 minutes 329 minutes 1.08 300 minutes 322 minutes 1.07
1.0V 318 minutes 338 minutes 1.06 314 minutes 331 minutes 1.05
From table 5a and 5b, can obviously find out, when the prior art with 22 μ m average particle size particle size contrasts FeS 2The coarse granule size FeS of particle and 75 μ m average particle size particle size 2When particle is compared, the FeS of working medium and jet grinding 2The battery of granulate preparation provides significantly long discharge time (to 1.05 volts).The FeS that contains medium milling 2Battery for also having kept cut-ff voltage more than or equal to 1.2 (volts) more than or equal to 1 volt situation average 69.6% running time, and control group is only to having kept above-mentioned voltage average 58.9% running time.Equally, the FeS that contains jet grinding 2Battery is for having kept cut-ff voltage more than or equal to 1.2 (volts) more than or equal to 1 volt situation 85.7% discharge time.
Embodiment 8
Structure has FR6 type cylindrical lithium/FeS that spiral twines electrode assemblie 2Battery.Mean F eS 2The thickness of particle size, electrolyte composition and separator is with changing described in the table 6.With the technique change of expecting, all the other battery characteristics are described identical with table 3 batch D except that typical.Battery 1-4 represents the prior art battery.Table 6 *(calculating estimated value)
2/28 second * 10/ hour DSC test is tested each battery to utilize 1500/650mW.Electrolyte-separator resistance and FeS 2Acting among Fig. 4 of particle size set forth.The curve chart of each battery batch set forth separator thickness reduce, use less average particle size particle size FeS 2Particle and electrolytical type be the influence of target efficient respectively.In Fig. 4, nethermost line (lower most line) has been represented the curve chart of line of best fit of the result of the test of battery 1-4.Remaining line equally, has from bottom to top been represented the result of battery 5-8,9-12 and 13-16 respectively.
Embodiment 9
In battery makes the time limit in week, measure and have FR6 type cylindrical lithium/FeS that spiral twines electrode assemblie 2The anode voltage of battery.Battery has the substantially the same structure described in batch D with table 3, and difference is the FeS of a kind of battery by 22 μ m 2The average grain structure, second kind of battery uses the FeS of average-size as the medium milling of 5-10 μ m (calculating valuation) 2Particle and the third battery use the FeS of the jet grinding of average-size 4.9 μ m 2Particle and process variations scheme typical and expection.As the function of depth of discharge as shown in Figure 5, to the anode voltage mapping of each battery.In Fig. 6, the full cell voltage as the function of depth of discharge is mapped.Test program is described hereinbefore.
Under 50% depth of discharge, when average particle size particle size when 22 μ m reduce to 5.2 μ m, anode voltage has reduced 40 millivolts.FeS 2Average particle size particle size is reduced to 4.9 μ m from 22 μ m makes anode voltage reduce 150 millivolts.Construct and test the L92 electrochemical cell in a similar manner.Find to use the FeS of average particle size particle size disclosed herein 2,, improved total cell voltage being independent of under any given depth of discharge of battery sizes.
Embodiment 10
FeS 2Average particle size particle size though under standard ambient condition, influence high battery performance strongly, has even bigger influence at low temperatures.Following table 7 has compared two kinds of different researchs, and average particle size particle size is negative electrode and the contrast FeS of average particle size particle size 22 μ m of the medium milling of 5-10 μ m (calculating valuation) 2, and battery performance is as the function of temperature.With the process variations scheme of expecting, construct battery except that typical with the said substantially the same mode of table 3 batch D.This test is like the proposed standard analog D SC-ANSI application of preceding (1500mW/650mW) that limits to 1.05 volts.Reduce particle size and under environmental condition, improved performance 5% or bigger, and under-20 ℃, observe improvement more than 600%.Table 7
Contrast Medium milling The performance ratio Contrast Medium milling The performance ratio
Temperature Minute Minute Minute Minute
21℃ 304 325 1.07 302 318 1.05
0℃ 178 227 1.27 186 121 1.14
-20℃ 14 102 7.28 16 100 6.25
The people of embodiment of the present invention with skilled person will appreciate that under the condition of the spirit that does not deviate from disclosed scheme and can carry out various changes and improvement the present invention.

Claims (15)

1. electrochemical cell, it comprises:
Shell;
Negative pole, it comprises lithium;
Positive pole, it comprises active material, and said active material comprises the ferrous disulfide greater than 49wt%;
Electrolyte mixture, it comprises at least a salt that places the nonaqueous electrolyte in the shell that is dissolved in; With
Separator, it places between negative pole and the positive pole, wherein
B) electrolytical conductivity is 1-19 μ m greater than the average diameter of the volume distributed median of 2.5mS/cm and ferrous disulfide; Or
C) separator thickness is that the average diameter of the volume distributed median of 1-25 μ m and ferrous disulfide is 1-19 μ m.
2. according to the battery of claim 1, wherein the conductivity of electrolyte mixture is greater than 4mS/cm.
3. according to the battery of claim 1, wherein the conductivity of electrolyte mixture is greater than 6mS/cm.
4. according to the battery of claim 2 or 3, wherein separator thickness is 5-20 μ m.
5. according to the battery of claim 2 or 3, wherein separator thickness is 10-20 μ m.
6. according to the battery of claim 1, wherein separator thickness is 10-16 μ m, and wherein the conductivity of electrolyte mixture greater than 6mS/cm.
7. according to the battery of claim 1; Wherein electrolytic salt comprises trifluoromethyl sulfonic acid lithium or lithium iodide; And wherein nonaqueous electrolyte comprises 1; 3-dioxolanes, 1,2-diethoxyethane and 3,5-dimethyl different
Figure FSB00000460878800011
azoles.
8. according to claim 2,3 or 6 battery; Wherein electrolytic salt comprises lithium iodide; And wherein nonaqueous electrolyte comprises 1; 3-dioxolanes, 1,2-diethoxyethane and 3,5-dimethyl different
Figure FSB00000460878800012
azoles.
9. according to claim 2,3 or 6 battery, the average diameter of the volume distributed median of wherein said ferrous disulfide is 2-15 μ m.
10. according to claim 2,3 or 6 battery, the average diameter of the volume distributed median of wherein said ferrous disulfide is 2-6 μ m.
11. according to the battery of claim 9, wherein separator thickness is 5-20 μ m.
12. according to the battery of claim 9, wherein separator thickness is 10-16 μ m.
13., wherein use 5mA/cm in room temperature according to the battery of claim 1 2Current density and under 1 ampere of work 2 minutes and 0 ampere of condition of working 5 minutes, make the battery periodic duty, under 50% depth of discharge, the anode voltage of battery is less than 190mV.
14., wherein use 5mA/cm in room temperature according to the battery of claim 1 2Current density and under 1 ampere of work 2 minutes and 0 ampere of condition of working 5 minutes, make the battery periodic duty, under 50% depth of discharge, the anode voltage of battery is less than 170mV.
15., wherein use 5mA/cm in room temperature according to the battery of claim 1 2Current density and under 1 ampere of work 2 minutes and 0 ampere of condition of working 5 minutes, make the battery periodic duty, under 50% depth of discharge, the anode voltage of battery is less than 100mV.
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